WO2018101083A1 - Corps stratifié et dispositif comprenant ledit corps - Google Patents

Corps stratifié et dispositif comprenant ledit corps Download PDF

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Publication number
WO2018101083A1
WO2018101083A1 PCT/JP2017/041451 JP2017041451W WO2018101083A1 WO 2018101083 A1 WO2018101083 A1 WO 2018101083A1 JP 2017041451 W JP2017041451 W JP 2017041451W WO 2018101083 A1 WO2018101083 A1 WO 2018101083A1
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film
layer
inorganic thin
thin film
gas barrier
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PCT/JP2017/041451
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English (en)
Japanese (ja)
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伊藤　豊
山下　恭弘
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住友化学株式会社
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Priority to KR1020197018719A priority Critical patent/KR102381205B1/ko
Priority to CN201780070736.8A priority patent/CN109952198B/zh
Publication of WO2018101083A1 publication Critical patent/WO2018101083A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/203—Adhesives in the form of films or foils characterised by their carriers characterised by the structure of the release feature on the carrier layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment

Definitions

  • the present invention relates to a laminate, and more particularly to a laminate comprising a gas barrier film used for a device and an adhesive layer.
  • Patent Document 1 a gas barrier adhesive sheet having a gas barrier layer and an adhesive layer has been proposed.
  • Patent Document 2 the manufacturing method of the laminated body which has a laminated film and the contact bonding layer formed in the one surface side of the laminated film is known (patent document 2).
  • a laminate comprising a laminated film in which a gas barrier film and an adhesive layer are formed may have a peelable film on the adhesive layer for the purpose of surface protection on both surfaces.
  • the laminate is peeled off the peelable film and bonded to the device via the exposed pressure-sensitive adhesive layer.
  • the peelable film on the side opposite to the pressure-sensitive adhesive layer side may be peeled off, bubbles may be generated, or the gas barrier film may be broken, resulting in a device failure. is there.
  • the present invention includes the following preferred embodiments.
  • the gas barrier film has a base material layer including at least a flexible base material, and an inorganic thin film layer on one surface of the base material layer, Formula (1): F1 ⁇ F2 (1) (In Formula (1), F1 represents the peel strength between the peelable film 1 and the gas barrier film, and F2 represents the peel strength between the peelable film 2 and the pressure-sensitive adhesive layer) And formula (2): G1 / G2 ⁇ 0.4 (2) (In Formula (2), G1 represents the rigidity of the peelable film 1, and G2 represents the rigidity of the peelable film 2).
  • the inorganic thin film layer has an average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer represented by the formula (4): 0.10 ⁇ C / Si ⁇ 0.50 (4)
  • the laminate according to any one of [3] to [5], in the range of [7] The atomic ratio of silicon to the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer, In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the oxygen atomic ratio and the carbon atomic ratio, respectively, conditions (i) and (ii): (I) The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the formula (8) in a region of 90% or more in the film thickness direction of the inorganic thin film layer.
  • the yield in the bonding process between the display device and the laminate having the gas barrier film can be improved.
  • the typical sectional view of one form of the layered product of the present invention is shown. It is a schematic diagram which shows the manufacturing apparatus for manufacturing the gas barrier film in an Example. 6 is a graph showing XPS depth profile measurement results of an inorganic thin film layer in a gas barrier film obtained in Production Example 1.
  • the laminate of the present invention comprises a gas barrier film, a pressure-sensitive adhesive layer on one surface of the gas barrier film, a peelable film 1 on the other surface of the gas barrier film, and the gas barrier film side of the pressure-sensitive adhesive layer.
  • the gas barrier film includes a base material layer including at least a flexible base material, and an inorganic thin film layer on one surface of the base material layer. Is the body.
  • the gas barrier film has a base material layer including at least a flexible base material, and an inorganic thin film layer on one surface of the base material layer.
  • the inorganic thin film layer may be disposed on either the peelable film 1 side or the peelable film 2 side with respect to the flexible substrate, but the inorganic thin film layer may be disposed on the peelable film 2 side for sealing performance. From the point of view, it is preferable.
  • the base material layer should just contain a flexible base material at least.
  • a resin film containing at least one resin as a resin component can be used, and a colorless and transparent resin film is preferable.
  • resins that can be used for the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide resins; polycarbonate resins; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin; Polyether sulfide (PES). It can also be used.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin
  • polyamide resins polycarbonate resins
  • Polystyrene resin Polyvin
  • the flexible substrate may be an unstretched resin film, and the unstretched resin substrate is uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch, tubular-type simultaneous biaxial stretch, etc.
  • the resin film may be stretched in the flow direction of the resin base material (MD direction) and / or the direction perpendicular to the flow direction of the resin base material (TD direction) by the known method.
  • the thickness of the flexible substrate can be appropriately set in consideration of the production of a stable laminate.
  • the thickness is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, and still more preferably 50 to 100 ⁇ m.
  • the layer constituting the flexible substrate may be a retardation film having different in-plane two-component refractive indexes such as a ⁇ / 4 retardation film and a ⁇ / 2 retardation film.
  • cellulose resin, polycarbonate resin, polyarylate resin, polyester resin, acrylic resin, polysulfone resin, polyethersulfone resin, cyclic olefin resin, alignment solidification of liquid crystal compound A layer etc. can be illustrated.
  • polycarbonate resin films are preferably used because they are inexpensive and uniform.
  • a film forming method a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used in terms of uniformity.
  • the stretching method is not particularly limited, and roll-to-roll longitudinal uniaxial stretching, tenter transverse uniaxial stretching, and the like that can obtain uniform optical properties can be applied.
  • the in-plane retardation Re (550) at a wavelength of 550 nm can be 100 to 180 nm, preferably 110 to 170 nm. More preferably, it is 120 to 160 nm.
  • the in-plane retardation Re (550) at a wavelength of 550 nm can be 220 to 320 nm, preferably 240 to 300 nm. More preferably, it is 250 to 280 nm.
  • the flexible substrate When the flexible substrate is a retardation film, it may exhibit reverse wavelength dispersion in which the retardation value increases according to the wavelength of the measurement light, and the retardation value decreases according to the wavelength of the measurement light.
  • a positive chromatic dispersion characteristic may be exhibited, or a flat chromatic dispersion characteristic in which the retardation value hardly changes depending on the wavelength of the measurement light may be exhibited.
  • the flexible substrate is a retardation film exhibiting reverse wavelength dispersion
  • the retardation at the wavelength ⁇ of the flexible substrate is expressed as Re ( ⁇ )
  • the flexible substrate 10 is Re (450) / Re (550) ⁇ 1 and Re (650) / Re (550)> 1 can be satisfied.
  • the flexible base material is preferably colorless and transparent from the viewpoint that light can be transmitted and absorbed. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
  • the flexible base material is preferably insulative from the viewpoint that it can be used as a base material for organic or energy devices, and preferably has an electrical resistivity of 10 6 ⁇ cm or more.
  • the base material layer may include the same or different kinds of organic layers A on at least one surface of the flexible base material for the purpose of improving the adhesion and / or flatness with the inorganic thin film layer.
  • organic layer A include a planarization layer, an easy slip layer, and an anti-blocking layer.
  • the base material layer When the base material layer includes the organic layer A, the base material layer has an organic layer only on one surface of the flexible base material, or different types of the base material layer on both surfaces of the flexible base material. It may have an organic layer, for example, a flat layer on one surface and a slippery layer on the other surface.
  • a resin composition containing a monomer and / or oligomer of a photocurable resin such as an ultraviolet ray or an electron beam curable resin is usually applied on a flexible substrate, and if necessary, dried. It can be formed by being cured by irradiation with ultraviolet rays or electron beams.
  • the resin composition may contain additives such as a solvent, a photopolymerization initiator, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, and a plasticizer as necessary.
  • Examples of methods by coating include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, gravure coating, Examples of the method include extrusion coating.
  • an acrylate resin can be used.
  • the acrylate resin is preferably a photocurable resin.
  • the photocurable resin is a resin that starts to be polymerized by ultraviolet rays, electron beams, or the like and cures.
  • a resin other than the acrylate resin may be included to the extent that the effect is not impaired.
  • Specific examples include polyester resins, isocyanate resins, ethylene vinyl alcohol resins, vinyl-modified resins, epoxy resins, phenol resins, urea melamine resins, styrene resins, and alkyl titanates, which contain one or more of these in combination. But you can.
  • the flatness of the surface can be improved by changing the drying conditions and curing conditions of the flattening layer, and it can also be used as an easy-sliding layer or an antiblocking layer.
  • the flattening layer when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.), the flattening layer surface It is preferable that the temperature at which the elastic modulus is reduced by 50% or more is 150 ° C. or more.
  • a resin composition containing inorganic particles can be used.
  • the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide.
  • the organic layer A is a slippery layer, the laminate can be easily conveyed by a roll.
  • a resin composition containing inorganic particles can be used.
  • the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, and zirconium oxide.
  • inorganic thin film layer As the inorganic thin film layer, a known inorganic material layer having gas barrier properties can be appropriately used. Examples of inorganic materials are metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, and mixtures containing at least two of these. Further, as the inorganic material layer, a multilayer film in which two or more inorganic thin film layers described above are stacked can be used. Further, the step of forming the inorganic thin film layer may be performed once or may be performed a plurality of times. When performed several times, it may be performed under the same conditions or may be performed under different conditions. Moreover, an inorganic thin film layer can be provided in the surface of one or both of a base material layer.
  • the inorganic thin film layer has at least silicon atoms (Si) and oxygen atoms (O) from the viewpoints of exhibiting a higher level of water vapor permeation prevention performance, and bending resistance, ease of production, and low production cost. , And a carbon atom (C).
  • the inorganic thin film layer may be mainly composed of a compound represented by the general formula SiO ⁇ C ⁇ (wherein ⁇ and ⁇ independently represent a positive number less than 2).
  • the main component means that the content of the component is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more with respect to the mass of all components constituting the inorganic thin film layer. It means that.
  • Inorganic thin layer may contain one kind of compound represented by the general formula SiO ⁇ C ⁇ , may contain a general formula SiO alpha C beta in two or more compounds represented.
  • One or more of ⁇ and ⁇ in the general formula may be a constant value or may vary in the thickness direction of the inorganic thin film layer.
  • the inorganic thin film layer contains an element other than silicon atom, oxygen atom and carbon atom such as hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. You may contain.
  • the inorganic thin film layer has a high density when the average atomic ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed by C / Si, and defects such as fine voids and cracks
  • the range of C / Si preferably satisfies the formula (4). 0.10 ⁇ C / Si ⁇ 0.50 (4) Further, it is more preferably in the range of 0.15 ⁇ C / Si ⁇ 0.45, more preferably in the range of 0.20 ⁇ C / Si ⁇ 0.40, and 0.25 ⁇ C / Si ⁇ 0. A range of 35 is particularly preferred.
  • the inorganic thin film layer has a high density when the average atomic ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed by O / Si, and fine voids, cracks, etc.
  • O oxygen atoms
  • Si silicon atoms
  • it is preferably in the range of 1.50 ⁇ O / Si ⁇ 1.90, more preferably in the range of 1.55 ⁇ O / Si ⁇ 1.85, and 1.60 ⁇ O. /Si ⁇ 1.80 is more preferable, and 1.65 ⁇ O / Si ⁇ 1.75 is particularly preferable.
  • the average atomic number ratios C / Si and O / Si are measured by XPS depth profile under the following conditions. From the obtained distribution curves of silicon atoms, oxygen atoms and carbon atoms, the averages in the thickness direction of the respective atoms. After obtaining the atomic concentration, the average atomic ratio C / Si and O / Si can be calculated.
  • the inorganic thin film layer has a peak intensity (I 1 ) existing at 950 to 1050 cm ⁇ 1 and a peak existing at 1240 to 1290 cm ⁇ 1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer.
  • the intensity ratio with the intensity (I 2 ) may be in a range satisfying the formula (5). 0.01 ⁇ I 2 / I 1 ⁇ 0.05 (5)
  • the peak intensity ratio I 2 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—CH 3 to Si—O—Si in the inorganic thin film layer.
  • the inorganic thin film layer satisfying the relationship represented by the formula (5) has high denseness and less defects such as fine voids and cracks, so that it is considered to have excellent gas barrier properties and excellent impact resistance. It is done.
  • the range of the peak intensity ratio I 2 / I 1, from the viewpoint of maintaining a high density of the inorganic thin layer preferably in the range of 0.02 ⁇ I 2 / I 1 ⁇ 0.04.
  • Infrared spectroscopic measurement of the surface of an inorganic thin film layer is a Fourier transform infrared spectrophotometer (FT / IR-460Plus, JASCO Corporation) equipped with an ATR attachment (PIKEPMIRacle) using a germanium crystal as a prism. Can be measured.
  • FT / IR-460Plus a Fourier transform infrared spectrophotometer
  • PIKEPMIRacle ATR attachment
  • the inorganic thin film layer has a peak intensity (I 1 ) existing at 950 to 1050 cm ⁇ 1 and a peak existing at 770 to 830 cm ⁇ 1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer.
  • the intensity ratio with the intensity (I 3 ) may be in the range of the formula (6). 0.25 ⁇ I 3 / I 1 ⁇ 0.50 (6)
  • the peak intensity ratio I 3 / I 1 calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .
  • the inorganic thin film layer satisfying the relationship represented by the formula (6) is considered to have excellent flex resistance and excellent impact resistance since carbon is introduced while maintaining high density.
  • the range of the peak intensity ratio I 3 / I 1 the range of 0.25 ⁇ I 3 / I 1 ⁇ 0.50 is preferable from the viewpoint of maintaining a balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.30
  • the range of ⁇ I 3 / I 1 ⁇ 0.45 is more preferable.
  • the thin film layer when subjected to infrared spectrometry the inorganic thin film layer surface (ATR method), a peak exists in the 770 ⁇ 830 cm -1 intensity (I 3), peaks at 870 ⁇ 910 cm -1
  • the intensity ratio with the intensity (I 4 ) may be in the range of the formula (7). 0.70 ⁇ I 4 / I 3 ⁇ 1.00 (7)
  • the peak intensity ratio I 4 / I 3 calculated from the infrared spectroscopic measurement (ATR method) is considered to represent the ratio between peaks related to Si—C in the inorganic thin film layer.
  • the inorganic thin film layer satisfying the relationship represented by the formula (7) is considered to have excellent flex resistance and excellent impact resistance since carbon is introduced while maintaining high density.
  • the range of the peak intensity ratio I 4 / I 3 the range of 0.70 ⁇ I 4 / I 3 ⁇ 1.00 is preferable from the viewpoint of maintaining the balance between the denseness and the bending resistance of the inorganic thin film layer, and 0.80
  • the range of ⁇ I 4 / I 3 ⁇ 0.95 is more preferable.
  • the thickness of the inorganic thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to break when the inorganic thin film layer is bent. Further, when the inorganic thin film layer is formed by plasma CVD using glow discharge plasma, the inorganic thin film layer is formed while discharging through the substrate. More preferably, it is ⁇ 1000 nm.
  • the average density of the inorganic thin film layer may be 1.8 g / cm 3 or more.
  • the “average density” of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms and the number of oxygen atoms obtained by Rutherford Backscattering Spectrometry (RBS), and the hydrogen forward scattering method (Hydrogen Forward Scattering Method). Calculate the weight of the inorganic thin film layer in the measurement range from the number of hydrogen atoms determined by Spectrometry (HFS) and divide by the volume of the inorganic thin film layer in the measurement range (product of ion beam irradiation area and film thickness). Is required.
  • the inorganic thin film layer When the average density of the inorganic thin film layer is 1.8 g / cm 3 or more, the inorganic thin film layer has a high density and a structure with few defects such as fine voids and cracks. Further, when the inorganic thin film layer is composed of silicon atoms, oxygen atoms, carbon atoms and hydrogen atoms, the average density of the inorganic thin film layer is preferably less than 2.22 g / cm 3 .
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the atomic ratio of silicon atoms at each distance is referred to as a silicon distribution curve.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of oxygen atoms at each distance is referred to as an oxygen distribution curve.
  • a curve indicating the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of carbon atoms at each distance is referred to as a carbon distribution curve.
  • the atomic ratio of silicon atoms, the atomic ratio of oxygen atoms, and the atomic ratio of carbon atoms are from the surface of the inorganic thin film layer to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer. It means the ratio of the number of atoms at each distance.
  • the atomic ratio of carbon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer is continuous in the thickness direction of the inorganic thin film layer. It is preferable to change to.
  • the atomic ratio of the carbon atoms continuously changes in the thickness direction means that, for example, in the carbon distribution curve, the atomic ratio of the carbon atoms is a plurality of extreme values within a predetermined displacement range. It represents that the increase and decrease to give the continuity is repeated, and does not include a discontinuously changing portion, that is, the atomic ratio of carbon atoms does not increase or decrease monotonously.
  • a graph FIG. 3 showing the XPS depth profile measurement result of the inorganic thin film layer in the gas barrier film obtained in Production Example 1 described later.
  • the atomic ratio and carbon distribution curve obtained from the silicon distribution curve, oxygen distribution curve and carbon distribution curve in the inorganic thin film layer satisfy the conditions (i) and (ii). .
  • the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon satisfy the condition represented by the formula (8) in a region of 90% or more in the film thickness direction of the inorganic thin film layer.
  • the carbon distribution curve has at least one extreme value.
  • the carbon distribution curve of the inorganic thin film layer is preferably substantially continuous.
  • the carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, when the distance from the surface of the thin film layer in the film thickness direction is x [nm] and the atomic ratio of carbon is C, it is preferable to satisfy the formula (9).
  • the carbon distribution curve of the inorganic thin film layer preferably has at least one extreme value.
  • the extreme value here is the maximum value or the minimum value of the atomic ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction.
  • the extreme value is that when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed, the atomic ratio of the element changes from increasing to decreasing, or the atomic ratio of the element changes from decreasing to increasing. Is the value of the atomic ratio.
  • the extreme value can be obtained based on the atomic ratio measured at a plurality of measurement positions in the film thickness direction, for example.
  • the measurement position of the atomic ratio is set such that the interval in the film thickness direction is, for example, 20 nm or less.
  • the measurement results at three or more different measurement positions are compared for a discrete data group including the measurement results at each measurement position. It can be obtained by determining the position that starts or decreases or decreases.
  • the position indicating the extreme value can also be obtained, for example, by differentiating the approximate curve obtained from the discrete data group.
  • the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve has at least one extreme value as described above has an increase in the gas permeability after bending with respect to the gas permeability before bending. It becomes less compared with the case where it does not satisfy. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is reduced as compared with the case where the number of extreme values of the carbon distribution curve is one. .
  • the increase amount is larger than that in the case where the number of extreme values of the carbon distribution curve is two. Less.
  • the carbon distribution curve has two or more extreme values
  • the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extreme value, and the second pole adjacent to the first extreme value is preferably in the range of 1 nm to 200 nm, and more preferably in the range of 1 nm to 100 nm. preferable.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve of the inorganic thin film layer is preferably 0.01 or more.
  • the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is less than that in the case where the condition is not satisfied. That is, by satisfying the above conditions, an effect of suppressing a decrease in gas barrier properties due to bending can be obtained.
  • the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 0.02 or more, the above effect is enhanced, and when it is 0.03 or more, the above effect is further enhanced.
  • the gas barrier property of the inorganic thin film layer tends to improve as the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve decreases.
  • the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (3 at%). Is particularly preferred.
  • the total atomic ratio is preferably less than 0.05, more preferably less than 0.04, and particularly preferably less than 0.03.
  • the gas barrier property of the inorganic thin film layer can be made uniform and improved.
  • the substantially uniform composition means that in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve, the number of extreme values existing in each film thickness direction at any two points on the surface of the inorganic thin film layer. Are the same, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in each carbon distribution curve is the same or within 0.05.
  • the inorganic thin film layer formed so as to satisfy the above conditions can exhibit a gas barrier property required for a flexible electronic device using an organic EL element, for example.
  • Such an inorganic thin film layer containing silicon atoms, oxygen atoms and carbon atoms is preferably formed by a chemical vapor deposition method (CVD method), and among them, a plasma chemical vapor deposition method using glow discharge plasma or the like. More preferably, it is formed by (PECVD method).
  • CVD method chemical vapor deposition method
  • PECVD method plasma chemical vapor deposition method using glow discharge plasma or the like. More preferably, it is formed by (PECVD method).
  • Examples of source gases include organosilicon compounds containing silicon atoms and carbon atoms.
  • organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propyl Examples include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane.
  • organosilicon compounds hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the obtained inorganic thin film layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
  • a reaction gas that can react with the source gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the source gas.
  • a reaction gas for forming an oxide for example, oxygen or ozone can be used.
  • a reactive gas for forming nitride nitrogen and ammonia can be used, for example.
  • These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and the nitride are formed. Can be used in combination with the reaction gas for The flow rate ratio between the source gas and the reaction gas can be adjusted as appropriate according to the atomic ratio of the inorganic material to be deposited.
  • the value of C / Si can be controlled by adjusting the flow ratio of the source gas and the reaction gas.
  • HMDSO hexamethyldisiloxane
  • oxygen used as the reaction gas
  • the ratio of the oxygen flow rate to the HMDSO flow rate O 2 / HMDSO is in the range of 5 to 25, and the value of C / Si is It can be controlled within the above-mentioned range.
  • a carrier gas may be used as necessary.
  • a discharge gas may be used as necessary.
  • carrier gas and discharge gas known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.
  • the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 50 Pa.
  • FIG. 2 is a schematic view showing an example of a manufacturing apparatus used for manufacturing an inorganic thin film layer included in a gas barrier film, and is a schematic view of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method.
  • the manufacturing apparatus shown in FIG. 2 is a magnetic field forming apparatus installed in each of a feed roll 11, a take-up roll 71, transport rolls 21 to 24, a gas supply pipe 41, a plasma generating power source 51, and film forming rolls 31 and 32. 61 and 62 are included.
  • the film forming rolls 31 and 32 also serve as electrodes and are roll electrodes described later.
  • At least the film forming roll, the gas supply pipe, and the magnetic field forming apparatus are disposed in a vacuum chamber (not shown) when forming the inorganic thin film layer.
  • This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.
  • Plasma CVD film formation can be performed by a continuous film formation process using plasma.
  • the delivery roll is installed in a state where the film 100 before film formation is wound up, and the film is sent out while being unwound in the longitudinal direction. Further, a winding roll is provided on the end side of the film, and the film after film formation is wound while being pulled and accommodated in a roll shape.
  • the two film forming rolls extend in parallel and face each other. Both rolls are formed of a conductive material and convey the film while rotating respectively.
  • the two film forming rolls preferably have the same diameter, for example, preferably 5 cm or more and 100 cm or less.
  • the base material layer When forming the inorganic thin film layer, the base material layer is transported in close contact with the surface of the pair of roll electrodes, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma to be flexible. It is preferable to form an inorganic thin film layer on a base material.
  • a magnet In the pair of electrodes, a magnet is preferably disposed inside the electrodes so that the magnetic flux density is high on the surfaces of the electrodes and the flexible substrate. As a result, the plasma tends to be constrained at a high density on the electrode and the flexible substrate when the plasma is generated.
  • the gas barrier film may have an organic layer B as the outermost layer of the gas barrier film.
  • the organic layer B includes an ultraviolet blocking layer, a matting agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, and an antifouling layer. Examples thereof include a hard coat layer such as a layer, a printing layer, and an easy adhesion layer.
  • the organic layer B may be laminated
  • the gas barrier film of the present invention preferably further has an organic layer B on the surface of the inorganic thin film layer opposite to the base material layer from the viewpoint of water vapor barrier properties.
  • Examples of the organic layer B include a layer composed of the resin described for the organic layer A in the above, a layer containing an additive for giving each function to the resin described for the organic layer A, and the like.
  • the film is appropriately selected depending on the use and usage of the conductive film.
  • Examples of the method for laminating the organic layer B include the methods described above for the organic layer A.
  • the organic layer B may be a layer formed using a composition containing an inorganic polymer such as polysilazane.
  • an inorganic polymer such as polysilazane.
  • the inorganic polymer layer can be adjusted to a desired film thickness by a single application, or can be adjusted to a desired film thickness by applying a plurality of times. In the case of applying a plurality of times, it is more effective to carry out the curing process for each application from the viewpoint of securing a diffusion path of gas generated by curing and correcting defects such as cracks.
  • the inorganic polymer layer can be formed by applying a coating liquid containing an inorganic polymer such as polysilazane on the inorganic thin film layer and drying it, followed by curing the formed coating film.
  • a coating liquid containing an inorganic polymer such as polysilazane
  • the coating solution a solution obtained by dissolving or dispersing an inorganic polymer in a solvent can be used.
  • concentration of the inorganic polymer in the coating solution may be appropriately adjusted according to the thickness of the inorganic polymer layer and the pot life requirement of the coating solution, but is usually 0.2 to 35% by mass.
  • examples of the polysilazane that is an inorganic polymer include perhydropolysilazane (PHPS).
  • PHPS perhydropolysilazane
  • the solvent a solvent that does not react with the inorganic polymer to be used, is suitable for dissolving or dispersing the inorganic polymer, and does not adversely affect the inorganic thin film layer can be appropriately selected and used.
  • the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers.
  • examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, toluene and xylene, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These solvents may be used as a mixture of two or more.
  • an amine catalyst When polysilazane is used as the inorganic polymer, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate is used in the coating solution to promote modification to silicon oxynitride.
  • a metal catalyst such as can also be added.
  • the amount of the catalyst added to the polysilazane is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.5 to 2% by mass based on the total amount of the coating solution. More preferably. By setting the addition amount of the catalyst within the above range, it is possible to suppress excessive silanol formation, film density reduction, film defect increase, and the like due to rapid progress of the reaction.
  • Drying may be performed under conditions that can remove the solvent in the coating solution. Further, for example, the coating liquid may be applied and dried simultaneously on a heated hot plate.
  • Examples of the curing method for the formed coating film include curing the inorganic polymer in the coating film, such as plasma CVD, ion implantation, ultraviolet irradiation, vacuum ultraviolet irradiation, oxygen plasma irradiation, and heat treatment. Can be used. Among these, it is preferable to use a method of irradiating the coating film with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less as a curing method. Moreover, the method of irradiating a coating film with vacuum ultraviolet light is more preferable when polysilazane is used as an inorganic polymer.
  • VUV light vacuum ultraviolet light
  • the coating film contains silanol groups, and there are cases where 2 ⁇ x ⁇ 2.5.
  • y is basically 1 or less because nitriding is generally unlikely to proceed more than the oxidation of Si.
  • Si—H and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation with vacuum ultraviolet irradiation, etc. It is considered that it is recombined as -N (an Si dangling bond may be formed). That is, perhydropolysilazane is cured as a SiN y composition without being oxidized. In this case, cleavage of the polymer main chain does not occur. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. Cut H is released into the epidural as H 2.
  • Si—O—Si Bonds by Hydrolysis and Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH.
  • Two Si—OH are dehydrated and condensed to form a Si—O—Si bond and harden. This is a reaction that occurs even in the atmosphere, but during vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated as outgas from the resin base material by the heat of irradiation becomes the main moisture source.
  • Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO 2.1 to SiO 2.3 is obtained.
  • composition of the silicon oxynitride of the layer obtained by subjecting the coating film containing polysilazane to vacuum ultraviolet irradiation is adjusted by appropriately combining the oxidation mechanisms (1) to (4) described above to control the oxidation state. It can be carried out.
  • intensity of the vacuum ultraviolet rays in the coated surface of the coating film containing polysilazane is subjected is preferably in the range of 1 ⁇ 100000mW / cm 2, it is within the range of 30 ⁇ 200mW / cm 2 It is more preferable. If the illuminance is 1 mW / cm 2 or more, there is no concern about the reduction of the reforming efficiency, and if it is 100000 mW / cm 2 or less, the coating film is not ablated and damages the flexible substrate. It is preferable because it is not present.
  • the integrated light amount (integrated irradiation energy amount) of vacuum ultraviolet rays irradiated to the coating film containing polysilazane is 1.0 to 100 mJ / in the following formula normalized by the film thickness of the inorganic polymer layer. preferably cm 2 / nm is in the range of 1.5 to more preferably in the range of 30mJ / cm 2 / nm, still in the range of 2.0 ⁇ 20mJ / cm 2 / nm A range of 5.0 to 20 mJ / cm 2 / nm is particularly preferable.
  • the normalized integrated light quantity is 1.0 mJ / cm 2 / nm or more, the modification can be sufficiently performed.
  • the normalized integrated light quantity is 100 mJ / cm 2 / nm or less, the excessive reforming condition is not achieved, and cracks in the inorganic polymer layer can be prevented. Even when the inorganic polymer layer is cured a plurality of times in order to obtain a desired film thickness, it is preferable that the standardized integrated light amount is within the range for each layer.
  • a rare gas excimer lamp is preferably used as the vacuum ultraviolet light source.
  • Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.
  • excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms.
  • the rare gas is xenon, e + Xe ⁇ Xe * Xe * + 2Xe ⁇ Xe 2 * + Xe Xe 2 * ⁇ Xe + Xe + h ⁇ (172 nm)
  • excimer light having a wavelength of 172 nm is emitted.
  • ⁇ Excimer lamps are characterized by high efficiency because radiation concentrates on one wavelength and almost no other light is emitted. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.
  • Dielectric barrier discharge is a gas space that is generated in a gas space by applying a high frequency high voltage of several tens of kHz to the electrode by placing a gas space between both electrodes via a dielectric such as transparent quartz. This discharge is called a micro discharge (micro discharge). When the micro discharge streamer reaches the tube wall (derivative), the electric charge accumulates on the dielectric surface, and the micro discharge disappears.
  • Electrodeless electric field discharge by capacitive coupling, also called RF discharge.
  • the lamp, the electrodes, and their arrangement may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.
  • an electrode in which fine metal wires are meshed is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.
  • the outer diameter of the double-cylindrical lamp is about 25 mm, the difference in distance to the irradiation surface cannot be ignored directly below the lamp axis and on the side of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.
  • the biggest feature of the capillary excimer lamp is its simple structure.
  • the quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.
  • the outer diameter of the tube of the thin tube lamp is about 6-12mm. If it is too thick, a high voltage is required for starting.
  • either dielectric barrier discharge or electrodeless field discharge can be used.
  • the shape of the electrode the surface in contact with the lamp may be flat, but by setting the shape according to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. .
  • the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this excimer light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy of the active oxygen and ozone and the ultraviolet radiation, the polysilazane layer can be modified in a short time.
  • ⁇ Excimer lamps have high light generation efficiency and can be lit with low power. In addition, it emits energy in the ultraviolet region, that is, in a short wavelength range because it does not emit light of a long wavelength that causes a temperature increase due to light irradiation, and has a feature that suppresses an increase in the surface temperature of an irradiation object. . For this reason, it is suitable for the modification
  • the oxygen concentration at the time of irradiation with vacuum ultraviolet rays is preferably within the range of 10 to 100,000 volume ppm, more preferably within the range of 50 to 50,000 volume ppm, and even more preferably within the range of 100 to 10,000 volume ppm. is there.
  • the gas that satisfies the irradiation environment at the time of irradiation with vacuum ultraviolet rays it is preferable to use a dry inert gas, and among these, dry nitrogen gas is preferably used from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation environment and changing the flow rate ratio.
  • the coefficient of static friction between one surface of the gas barrier film and the other surface is 0.30 or more and 2.0 or less.
  • the static friction coefficient is determined by dividing a gas barrier film having an upper surface and a lower surface into two sheets and bringing the upper surface of the first gas barrier film and the lower surface of the second gas barrier film into contact with each other. What is necessary is just to measure a coefficient.
  • the coefficient of static friction can be measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH% in accordance with the gradient method of JIS P8147.
  • the surface roughness on both sides of the gas barrier film may be adjusted.
  • the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base material layer may be adjusted.
  • the surface roughness of the exposed surface of one inorganic thin film layer and the surface roughness of the exposed surface of the other inorganic thin film layer may be adjusted.
  • the surface roughness of at least one surface of the gas barrier film is increased, the static friction coefficient between the front and back surfaces tends to decrease.
  • the surface roughness of the inorganic thin film layer can be changed, for example, according to conditions such as the pressure in the vacuum chamber (vacuum degree) and the film thickness in the film forming conditions of the inorganic thin film layer, and the composition of the inorganic film forming layer.
  • the surface roughness of the inorganic thin film layer is adjusted by adjusting the surface roughness of the flexible base material serving as a base and the surface roughness of the intermediate layer disposed between the inorganic thin film layer and the flexible base material. Can also be adjusted.
  • a corona treatment or the like may be performed.
  • the arithmetic average roughness Ra of the surface of the inorganic thin film layer can be 3 nm or less.
  • the arithmetic average roughness Ra can be obtained by attaching the gas barrier film to an epoxy plate with an adhesive and then observing the surface with a white interference microscope.
  • the arithmetic average roughness Ra is an arithmetic average roughness according to JIS B 0601: 2001.
  • the average of the distances from the horizontal plane to the four corners is 2 mm or less.
  • This average value can be measured as follows. First, the gas barrier film is held for 48 hours under conditions of a temperature of 23 ° C. and a humidity of 50 RH%. Next, a 50 mm square part is cut out from the gas barrier film to obtain a sample. The sample is placed on the horizontal plane so that the center of the sample is in contact with the horizontal plane, and a total of four distances from the horizontal plane to the four corners are obtained. Finally, the average of these 4 points is obtained.
  • the stress of each inorganic thin film layer on the front and back surfaces or balance the stress between the inorganic thin film layer on one side and the coating layer below it. Or reducing the residual stress of the inorganic thin film layer itself, or combining these to balance the stress on both sides.
  • the stress can be adjusted by the film forming pressure and film thickness when forming the inorganic thin film layer, the degree of cure shrinkage when forming the coating layer, and the like.
  • the water vapor permeability of the gas barrier film at 40 ° C. and 90% RH can be 0.1 g / m 2 / day or less, and can be 0.001 g / m 2 / day or less.
  • the water vapor transmission rate can be measured by a Ca corrosion test method according to ISO / WD 15106-7 (Annex C).
  • the gas barrier film can be manufactured by a method in which the base material layer and the inorganic thin film layer are separately manufactured and bonded, a method in which the inorganic thin film layer is formed on the base material layer, and the like.
  • the inorganic thin film layer is formed on the flexible base material or the organic layer A laminated on the surface of the flexible base material by using a known vacuum film forming method such as a CVD method using glow discharge plasma. It is preferable to manufacture.
  • the organic layer B may be formed on the laminated film thus obtained by a known method.
  • the inorganic thin film layer is preferably formed by a continuous film forming process.
  • the inorganic thin film layer may be formed while the flexible substrate is conveyed from the feed roll to the take-up roll. Then, you may form an inorganic thin film layer from the top by inverting a sending roll and a winding roll, and conveying a base material in the reverse direction.
  • the pressure-sensitive adhesive layer is disposed on one surface of the gas barrier film.
  • the pressure-sensitive adhesive layer is not particularly limited as long as it can exhibit the function of adhering the gas barrier film to other members, but in addition to the commonly known adhesives and pressure-sensitive adhesives, adhesives and pressure-sensitive adhesives
  • a component that consumes moisture by reaction or a component that consumes moisture by reaction, or a component that consumes moisture by reaction can be used as an adhesive or a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer can also remove moisture adsorbed by drying. In that case, it is preferable that the pressure-sensitive adhesive layer be used in a dry state. The surface of the pressure-sensitive adhesive layer is peeled off as described below until it is used.
  • the adhesive film 2 is bonded together.
  • the peelable film 2 is disposed on the gas barrier film via the pressure-sensitive adhesive layer.
  • the peelable film 2 is peeled off, and the other member is bonded to the pressure-sensitive adhesive layer disposed on the surface of the gas barrier film. At this time, the pressure-sensitive adhesive layer does not peel from the gas barrier film when the peelable film 2 is peeled off.
  • the pressure-sensitive adhesive layer may be attached to an object by pressing called pressure-sensitive adhesive (Pressure ⁇ Sensitive Adhesive, PSA).
  • PSA Pressure ⁇ Sensitive Adhesive
  • pressure-sensitive adhesives known pressure-sensitive adhesives can be used, and adhesives that are “substances that are sticky at room temperature and adhere to adherends with light pressure” (JIS K 6800) are used. It is also possible to use a capsule that contains a specific component in a protective coating (microcapsule) and can maintain stability until the coating is destroyed by appropriate means (pressure, heat, etc.) (JIS K 6800). A mold adhesive may be used.
  • the pressure-sensitive adhesive layer has a polymerizable functional group remaining in the constituent resin composition, and after the gas barrier film is adhered to another member, the resin composition that constitutes the adhesive layer is further polymerized, thereby strengthening the adhesive layer. It is good also as a structure which implement
  • the pressure-sensitive adhesive layer may be configured to use a thermosetting resin composition or a photocurable resin composition as a material and polymerize and cure the resin by supplying energy afterwards.
  • the thickness of the pressure-sensitive adhesive layer can be 100 ⁇ m or less. Further, when the thickness of the pressure-sensitive adhesive layer is less than 10 ⁇ m, it is assumed that the impact resistance is lowered and wrinkles are likely to occur.
  • the pressure-sensitive adhesive layer may be composed of one layer, and may have a laminated structure that can be bonded on both sides by providing an adhesive layer on both sides of a film serving as a base material like a so-called double-sided tape. .
  • the peelable film 1 is detachably attached to the outermost layer on the gas barrier film side of the laminate of the present invention.
  • the peelable film 1 has a role as a protective film that protects the gas barrier film and other layers when the laminate is stored, transported, and the like, and has a role of providing support to the laminate.
  • the peelable film 1 is preferably a plastic film from the viewpoint of easily improving the surface protection of the laminate.
  • a plastic film from the viewpoint of easily improving the surface protection of the laminate.
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • acrylic resin polycarbonate
  • PC polycarbonate
  • resins may be used alone or in combination of two or more.
  • the peelable film 1 may be bonded to the surface of the laminate by electrostatic attraction or the like, or may be bonded to the surface of the laminate via an adhesive.
  • the adhesive for the protective film examples include acrylic resins, rubber resins, ethylene vinyl acetate copolymer resins, polyester resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, and polyimide resins. It is preferable to contain a polyolefin resin or the like as an adhesive. Moreover, the adhesive of a protective film may contain the other component of an adhesive, for example, an antistatic agent, a coloring agent, a ultraviolet absorber, etc.
  • the peelable film 1 has, for example, sufficient adhesiveness to maintain the state in which the peelable film 1 is bonded to the surface of the gas barrier film in the production process or distribution process, and the peelable film 1 from the surface of the laminate. It is required to have releasability that is easy to remove.
  • the peel strength F1 between the peelable film 1 and the gas barrier film is preferably 0.1 N / cm or more, more preferably. Is greater than 0.1 N / cm, more preferably 0.15 N / cm or more, and even more preferably 0.2 N / cm or more.
  • the peel strength F1 between the peelable film 1 and the gas barrier film is preferably 1.0 N. / Cm or less, more preferably 0.7 N / cm or less, still more preferably 0.5 N / cm or less.
  • the peel strength between the peelable film 1 and the gas barrier film was measured according to JIS K-6854-2.
  • the peelable film 1 preferably has a tensile elastic modulus of 100 MPa or more, more preferably 150 MPa or more, and even more preferably 200 MPa or more, from the viewpoint of easily improving the surface protection of the laminate. Moreover, the tensile elastic modulus of the peelable film 1 is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, and even more preferably 4,200 MPa or less, from the viewpoint of easy bonding.
  • the tensile elastic modulus of the peelable film can be measured by performing a tensile test using an electromechanical universal testing machine manufactured by Instron, in accordance with JIS K7127, using a test speed of 5 mm / min and a load cell of 5 kN. it can.
  • the average value of the film thickness of the peelable film 1 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more, from the viewpoint of easily improving the protection of the surface of the laminate. Moreover, the average value of the film thickness of the peelable film 1 is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and still more preferably 60 ⁇ m or less, from the viewpoint of easy bonding. The average value of the film thickness of the peelable film 1 is measured with a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.
  • the peelable film 2 is detachably attached to the surface of the pressure-sensitive adhesive layer of the laminate of the present invention.
  • the peelable film 2 has a role as a protective film that protects the pressure-sensitive adhesive layer and other layers when storing and transporting the laminate, and a role of providing support to the laminate.
  • the peelable film 2 is peeled off from the surface of the pressure-sensitive adhesive layer of the laminate in the manufacturing process of the display device, and the laminate is bonded to the display device via the pressure-sensitive adhesive layer and incorporated as a component of the display device. .
  • the peelable film 2 may be paper or a plastic film.
  • a release agent may be applied to the surface in order to enhance the peelability.
  • the peelable film 2 is preferably a plastic film from the viewpoint of easily improving the surface protection of the pressure-sensitive adhesive layer.
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • acrylic resin polycarbonate
  • PC polycarbonate
  • resin film containing a resin such as (PC) as a resin component may be used alone or in combination of two or more.
  • the peelable film 2 has, for example, sufficient adhesiveness to maintain the state in which the peelable film 2 is bonded to the surface of the pressure-sensitive adhesive layer in the production process or distribution process, and the peelable film 2 from the surface of the pressure-sensitive adhesive layer. It is required to have releasability that is easy to remove. From the viewpoint of easily maintaining the state where the peelable film 2 is bonded to the surface of the pressure-sensitive adhesive layer, the peel strength F2 between the peelable film 2 and the pressure-sensitive adhesive layer is preferably 0.05 N / cm or more, more preferably. Is a peel strength of 0.07 N / cm or more, more preferably 0.1 N / cm or more.
  • the peel strength F2 between the peelable film 2 and the pressure-sensitive adhesive layer is preferably 0.5 N / cm or less. More preferably, it is 0.4 N / cm or less, and still more preferably 0.3 N / cm or less.
  • the peel strength F2 is preferably lower than the peel strength F1 in order to prevent the peelable film 1 from being peeled when the peelable film 2 is peeled off in the bonding step with the display device.
  • the peel strength measurement between the peelable film 2 and the pressure-sensitive adhesive layer was carried out according to JIS K 6854-2.
  • the peelable film 2 preferably has a tensile elastic modulus of 100 MPa or more, more preferably 150 MPa or more, and even more preferably 200 MPa or more, from the viewpoint of easily improving the protection of the surface of the laminate. Further, the tensile elastic modulus of the peelable film 2 is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, and even more preferably 4,000 MPa or less, from the viewpoint of easy bonding.
  • the tensile elastic modulus of the peelable film can be measured by performing a tensile test using an electromechanical universal testing machine manufactured by Instron, in accordance with JIS K7127, using a test speed of 5 mm / min and a load cell of 5 kN. it can.
  • the average value of the film thickness of the peelable film 2 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more, from the viewpoint of easily improving the protection of the surface of the laminate. Moreover, the average value of the film thickness of the peelable film 2 is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and still more preferably 60 ⁇ m or less, from the viewpoint of easy bonding. The average value of the film thickness of the peelable film 2 is measured with a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.
  • the laminated body of this invention satisfy
  • F1 ⁇ F2 (1) In Formula (1), F1 represents the peel strength between the peelable film 1 and the gas barrier film, and F2 represents the peel strength between the peelable film 2 and the pressure-sensitive adhesive layer.
  • G1 / G2 ⁇ 0.4 (2) In Formula (2), G1 represents the rigidity of the peelable film 1, and G2 represents the rigidity of the peelable film 2.
  • the rigidity of the peelable film is represented by the formula (a).
  • G1 / G2 is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and particularly preferably 0.9 or more.
  • G1 / G2 is preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.0 or less.
  • the laminate of the present invention may be in the form of being rolled up or in the form of a sheet cut to a predetermined size.
  • the laminate of the present invention can be bonded to the display device via the pressure-sensitive adhesive layer by peeling the peelable film 2 and exposing the pressure-sensitive adhesive layer in the bonding step with the display device.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the resin laminate of the present invention.
  • This laminated body (10) has an adhesive layer (5) on a gas barrier film (4) in which an inorganic thin film layer (3) is formed on a flexible substrate (1) having an organic layer A (2).
  • the peelable film 1 (6) is stuck on the opposite side of the inorganic thin film layer (3), and the peelable film 2 (7) is stuck on the pressure-sensitive adhesive layer (5).
  • FIG. 1 is an example of the laminate of the present invention, and the laminate of the present invention is not limited to this configuration.
  • Examples of the layer structure of the laminate of the present invention include peelable film 2 / adhesive layer / inorganic thin film layer / organic layer A / flexible substrate / peelable film 1 layer structure, peelable film 2 / adhesive.
  • the laminate of the present invention can be produced by a known production method.
  • a manufacturing method the gas barrier film which has the peelable film 1, and the method of bonding the adhesive layer which has the peelable film 2, and the gas barrier film and the adhesive layer which has the peelable film 2 are stuck. Then, a method of sticking the peelable film 1 on the gas barrier film, a method of forming a pressure-sensitive adhesive layer on the gas barrier film having the peelable film 1, and then sticking the peelable film 2 to the pressure-sensitive adhesive layer And a method of forming a pressure-sensitive adhesive layer on the gas barrier film and then attaching the peelable film 1 and the peelable film 2 to each other.
  • the gas barrier film having the peelable film 1 and the pressure-sensitive adhesive layer having the peelable film 2 are bonded together, the gas barrier film and the pressure-sensitive adhesive layer having the peelable film 2 are bonded together, and then peeled off.
  • a method of sticking the adhesive film 1 on the gas barrier film and a method of forming an adhesive layer on the gas barrier film having the peelable film 1 and then sticking the peelable film 2 to the adhesive layer are preferable.
  • the other peelable film can be bonded to the surface of the exposed gas barrier film and the pressure-sensitive adhesive layer by peeling before the gas barrier film and the pressure-sensitive adhesive layer are bonded to each other.
  • the other peelable film and the gas barrier film may be attached via an adhesive.
  • peelable films and pressure-sensitive adhesives that can be used for the gas barrier film having the peelable film 1, those exemplified above for the peelable film 1 can be used.
  • the peel strength F1 ′ between the other peelable film and the gas barrier film is between the peelable film 1 and the gas barrier film.
  • the peel strength is preferably smaller than F1.
  • the pressure-sensitive adhesive layer having the peelable film 2 may further have another peelable film different from the peelable film 2 in addition to the peelable film 2 before being bonded to the gas barrier film.
  • the other peelable film can be bonded to the surface of the exposed pressure-sensitive adhesive layer and the gas barrier film by peeling before the gas barrier film and the pressure-sensitive adhesive layer are bonded together.
  • peelable film that can be used for the pressure-sensitive adhesive layer having the peelable film 2
  • those exemplified above for the peelable film 2 can be used.
  • the peel strength F2 ′ between the other peelable film and the pressure-sensitive adhesive layer is between the peelable film 2 and the pressure-sensitive adhesive layer.
  • the peel strength is preferably smaller than F2.
  • F2 ' is smaller than F2, it is possible to prevent the peelable film 2 from being peeled off or air bubbles from being generated when another peelable film is peeled from the pressure-sensitive adhesive layer.
  • Each of the peelable films 1 and 2 may be subjected to a known peeling treatment so that a desired peeling strength can be obtained.
  • Examples of the method for performing the release treatment include a method of applying a release agent to the surface of the release film.
  • the gas barrier film and the pressure-sensitive adhesive layer are bonded together while unwinding the gas barrier film wound in a roll shape and the pressure-sensitive adhesive layer wound in a roll shape, and then wound in a roll shape. It can also be performed in a roll-to-roll format, or can be cut to a desired size without being wound into a roll after being bonded.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is coated on the surface, the peelable film 2 is bonded, and then rolled in a roll-to-roll format. Can be rolled up or cut to the desired dimensions.
  • the present invention also provides a device having the laminate of the present invention, for example, a flexible electronic device.
  • the laminate of the present invention can also be used as a flexible substrate for flexible electronic devices (for example, flexible displays) such as liquid crystal display elements, solar cells, and organic EL displays.
  • Inorganic thin film layer thickness An inorganic thin film layer is formed on a flexible substrate, and a step difference measurement between the non-deposition part and the film formation part is performed using a surf coder ET200 manufactured by Kosaka Laboratory Co., Ltd. )
  • ⁇ X-ray photoelectron spectroscopy measurement on the surface of the inorganic thin film layer The atomic ratio of the inorganic thin film layer surface of the gas barrier film was measured by X-ray photoelectron spectroscopy (manufactured by ULVAC PHI, Quantera SXM).
  • An AlK ⁇ ray (1486.6 eV, X-ray spot 100 ⁇ m) was used as the X-ray source, and a neutralizing electron gun (1 eV) and a low-speed Ar ion gun (10 V) were used for charge correction during measurement.
  • the analysis after the measurement is performed by spectrum analysis using MultiPak V6.1A (ULVAC-PHI), and each binding of Si 2p, O 1s, N 1s and C 1s obtained from the measured wide scan spectrum. Using the peak corresponding to energy, the surface atom number ratio of C to Si was calculated. As the surface atom number ratio, an average value of values measured five times was adopted.
  • Infrared spectroscopic measurement of inorganic thin film layer surface is Fourier transform infrared spectrophotometer equipped with ATR attachment (PIKE MIRacle) using germanium crystal for prism (manufactured by JASCO Corporation, FT / IR- 460Plus).
  • PIKE MIRacle germanium crystal for prism
  • germanium crystal for prism manufactured by JASCO Corporation, FT / IR- 460Plus
  • a cyclocycloolefin film manufactured by ZEON Co., Ltd., ZEONOR (registered trademark) ZF16
  • the total light transmittance of the laminated film was measured by a direct reading haze computer (model HGM-2DP) manufactured by Suga Test Instruments Co., Ltd. After measuring the background in the absence of a sample, the laminated film was set on a sample holder and measured, and the total light transmittance was determined.
  • the gas barrier property of the laminated film was measured by a Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, and the water vapor permeability of the laminated film was obtained. .
  • the peelable sheet and the adherend were stuck so as not to contain air bubbles to obtain a release sheet / adhesive laminate.
  • This laminate was allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
  • the adherend is cut to a width of 20 mm, fixed to the SUS plate with an adhesive and fixed to the lower side of the tensile tester, the release sheet is bent 90 degrees, and fixed to the upper chuck of the tensile tester.
  • the peel strength was measured by peeling at a tensile rate of 0.3 m / min in an environment of a temperature of 23 ° C. and a humidity of 50% RH.
  • the thickness of the peelable film was an average value of measured values at arbitrary 10 points using a digital micrometer.
  • ⁇ Tensile modulus> The measurement was performed by performing a tensile test using an electromechanical universal testing machine manufactured by Instron in accordance with JIS K 7127 using a test speed of 5 mm / min and a load cell of 5 kN.
  • a gas barrier film was produced using the production apparatus shown in FIG. That is, the resin film substrate was attached to the delivery roll 11. And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to the film-forming roll 31 and the film-forming roll 32, respectively, In this discharge region, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a reactive gas) is generated in such a discharge region. And an inorganic thin film was formed by plasma CVD under the following conditions to obtain a gas barrier film.
  • HMDSO hexamethyldisiloxane
  • ⁇ Film formation conditions Source gas supply: 50 sccm (Standard Cubic Centimeter per Minute) Supply amount of oxygen gas: 500sccm Degree of vacuum in the vacuum chamber: 1Pa Applied power from power source for plasma generation: 0.4kW Power supply frequency for plasma generation: 70kHz Film transport speed: 0.6m / min Number of passes: 6
  • the infrared absorption spectrum did not change even when UV-O 3 treatment or atmospheric pressure plasma treatment described later was applied, and showed the above-mentioned absorption intensity ratio.
  • the obtained laminated film 1 is in the order of oxygen, silicon, and carbon in the order of larger atomic ratio in the region of 90% or more in the film thickness direction of the inorganic thin film layer, and the carbon distribution curve in the film thickness direction.
  • the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in the carbon distribution curve was 0.15 or more.
  • the thickness of the inorganic thin film layer in the obtained gas barrier film was 0.7 ⁇ m. Further, in the obtained gas barrier film, the water vapor permeability under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 ⁇ 10 ⁇ 5 g / (m 2 ⁇ day).
  • Example 1 Corona treatment on one side of a cycloolefin polymer film (COP film, thickness: 50 ⁇ m, width: 350 mm, made by Nippon Zeon Co., Ltd., trade name “Zeonor (registered trademark) film, ZF-16”), which is a flexible substrate
  • the coating agent 1 manufactured by Toyochem Co., Ltd., Rioduras TYAB500LC3NS, with particles
  • the organic layer A1 (slidable layer) having a thickness of 1.5 ⁇ m was laminated by irradiating with ultraviolet rays under the condition of / cm 2 .
  • coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toa Gosei Co., Ltd.) was applied by the gravure coating method and dried at 100 ° C. for 3 minutes.
  • UV irradiation is performed under the condition of an integrated light quantity of 500 mJ / cm 2 , and an organic layer A 2 (planarization layer) having a thickness of 1.8 ⁇ m is laminated to form a laminated film as a base material layer. Obtained.
  • the inorganic thin film layer 2 is laminated on the surface of the laminated film thus obtained on the organic layer A2 side under the conditions of Production Example 1, and further on the surface of the organic layer A1 side on the condition of Production Example 2 under the conditions of Production Example 2.
  • Layer 1 was laminated to produce a gas barrier film.
  • a transparent double-sided pressure-sensitive adhesive tape 1 (manufactured by Lintec Corporation, TL-430S-6, 30 ⁇ m thickness) was bonded as an adhesive layer to the surface of the inorganic thin film layer 2 of the gas barrier film.
  • a PET film Toyobo Co., Ltd., E5100, thickness: 38 ⁇ m
  • the finished surface was bonded to the adhesive layer.
  • a protective film 1 manufactured by Sanei Kaken Co., Ltd., SAT106T-JSL, PET 38 ⁇ m
  • Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material.
  • the ratio (yield) of the product obtained without producing the process defect was 95%.
  • Example 2 instead of the protective film 1, an acrylic adhesive layer adjusted to have a peeling force of 0.4 N / 20 mm with the inorganic thin film layer 1 is formed on a PET film (Toyobo Co., Ltd., E5100, thickness: 50 ⁇ m).
  • a laminate was produced in the same manner as in Example 1 except that the protective film 2 was used.
  • Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling process was implemented using the obtained laminated body, the ratio (yield) of the product obtained without producing the process defect was 100%.
  • Example 3 A laminate was produced in the same manner as in Example 1 except that the protective film 3 (manufactured by Sanei Kaken, NSA-35H, PET 50 ⁇ m) was used instead of the protective film 1.
  • Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling process was implemented using the obtained laminated body, the ratio (yield) of the product obtained without producing the process defect was 90%.
  • Example 1 As the peelable film 2, a PET film (Toyobo Co., Ltd., E5100, thickness: 100 ⁇ m) that has been subjected to a release treatment so that the peel strength from the pressure-sensitive adhesive layer is 0.2 N / 20 mm is bonded to the pressure-sensitive adhesive layer A laminated body was manufactured in the same manner as Example 1 except for the above. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling process was implemented using the obtained laminated body, the ratio (yield) of the product obtained without producing the process defect was 30%.
  • Example 2 In place of the protective film 1, a protective film 4 (manufactured by Sanei Kaken Co., Ltd., NSA-33T, PET 38 ⁇ m) was used, and the peelable film 2 was separated so that the peeling force with the adhesive layer was 0.4 N / 20 mm.
  • a laminate was produced in the same manner as in Example 1 except that the shape-treated PET film (E5100, manufactured by Toyobo Co., Ltd., thickness: 38 ⁇ m) was bonded to the adhesive layer.
  • Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling process was implemented using the obtained laminated body, the ratio (yield) of the product obtained without producing the process defect was 0%.
  • a protective film 6 (manufactured by Toray Film Processing Co., Ltd., 7332, PE, 50 ⁇ m) is used, and as the peelable film 2, the peeling force with the adhesive layer is 0.4 N / 20 mm.
  • a laminate was produced in the same manner as in Example 1 except that a release-treated PET film (Toyobo Co., Ltd., E5100, thickness: 38 ⁇ m) was bonded to the adhesive layer.
  • Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material.
  • the ratio (yield) of the product obtained without producing the process defect was 0%.
  • the peel strength F1 between the peelable film 1 and the gas barrier film is such that the peel strength between the peelable film 2 and the pressure-sensitive adhesive layer. Since it is F2 or more and the rigidity G1 of the peelable film 1 is more than the rigidity G2 of the peelable film 2, air bubbles or cracks in the gas barrier film are formed between the gas barrier film and the peelable film 1 in the peeling process. It was confirmed that the process defects such as the occurrence of slag were suppressed and the product yield was high. Therefore, it is understood that the laminate of the present invention is suitably used in a display device or the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Selon l'invention, dans des corps stratifiés comportant un film pelable sur la couche la plus à l'extérieur d'un film stratifié dans lequel un film barrière aux gaz et une couche adhésive sont stratifiés, le film pelable sur le côté opposé au côté de la couche adhésive peut se décoller, des bulles d'air peuvent être générées, ou le film barrière aux gaz peut se rompre lorsque le film pelable sur le côté de la couche adhésive est décollé. La présente invention concerne un corps stratifié comportant un film barrière aux gaz, une couche adhésive sur une surface du film barrière aux gaz, un film pelable 1 sur l'autre surface du film barrière aux gaz, et un film pelable 2 sur la surface de la couche adhésive opposée au film barrière aux gaz, le film barrière aux gaz comportant une couche de matériau de base comprenant au moins un matériau de base souple, et une couche de film mince inorganique sur une surface de la couche de matériau de base, et le corps stratifié satisfaisant les formules (1) et (2).
PCT/JP2017/041451 2016-11-29 2017-11-17 Corps stratifié et dispositif comprenant ledit corps WO2018101083A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021199798A1 (fr) * 2020-03-31 2021-10-07 東洋紡株式会社 Stratifié à base d'un substrat inorganique/film plastique technique équipé d'un film protecteur, empilement stratifié, procédé de stockage de stratifié, et procédé de transport de stratifié

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6920108B2 (ja) * 2017-05-31 2021-08-18 日東電工株式会社 光学フィルム、剥離方法及び光学表示パネルの製造方法
CN114728512A (zh) * 2019-12-06 2022-07-08 凸版印刷株式会社 阻气膜

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001064608A (ja) * 1999-09-01 2001-03-13 Nitto Denko Corp 無機薄膜積層体及び無機薄膜形成体
JP2008275722A (ja) * 2007-04-26 2008-11-13 Sumitomo Chemical Co Ltd 偏光板製品の梱包方法
WO2010026869A1 (fr) * 2008-09-02 2010-03-11 コニカミノルタホールディングス株式会社 Film composite, film barrière aux gaz et son procédé de production, et élément d’électroluminescence organique
WO2013018602A1 (fr) * 2011-08-03 2013-02-07 リンテック株式会社 Feuille adhésive dotée de propriétés de barrière aux gaz ainsi que procédé de fabrication de celle-ci, et élément électronique ainsi qu'élément optique
WO2015152302A1 (fr) * 2014-03-31 2015-10-08 コニカミノルタ株式会社 Film barrière contre les gaz, procédé de production associé, dispositif électronique utilisant ledit film et procédé de fabrication de dispositif électronique

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013103959A (ja) * 2011-11-11 2013-05-30 Furukawa Electric Co Ltd:The 半導体用接着シート
KR102058902B1 (ko) * 2012-03-27 2019-12-26 스미또모 가가꾸 가부시키가이샤 적층 필름, 유기 전계 발광 장치, 광전 변환 장치 및 액정 디스플레이
JP6170290B2 (ja) * 2012-10-11 2017-07-26 日東電工株式会社 積層体
JP5983454B2 (ja) * 2012-12-26 2016-08-31 コニカミノルタ株式会社 ガスバリア性フィルム
JP2014173011A (ja) * 2013-03-08 2014-09-22 Nitto Denko Corp 両面粘着テープ
CN103707565B (zh) * 2013-12-31 2017-11-24 北京维信诺科技有限公司 基板结构及其柔性衬底的贴附和剥离方法
KR102384767B1 (ko) 2014-09-08 2022-04-07 스미또모 가가꾸 가부시키가이샤 적층 필름 및 플렉시블 전자 디바이스
JP6638182B2 (ja) * 2014-09-30 2020-01-29 住友化学株式会社 積層フィルムおよびフレキシブル電子デバイス
JP5823591B1 (ja) * 2014-10-01 2015-11-25 古河電気工業株式会社 半導体ウエハ表面保護用粘着テープおよび半導体ウエハの加工方法
JP6342776B2 (ja) 2014-10-09 2018-06-13 住友化学株式会社 積層体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001064608A (ja) * 1999-09-01 2001-03-13 Nitto Denko Corp 無機薄膜積層体及び無機薄膜形成体
JP2008275722A (ja) * 2007-04-26 2008-11-13 Sumitomo Chemical Co Ltd 偏光板製品の梱包方法
WO2010026869A1 (fr) * 2008-09-02 2010-03-11 コニカミノルタホールディングス株式会社 Film composite, film barrière aux gaz et son procédé de production, et élément d’électroluminescence organique
WO2013018602A1 (fr) * 2011-08-03 2013-02-07 リンテック株式会社 Feuille adhésive dotée de propriétés de barrière aux gaz ainsi que procédé de fabrication de celle-ci, et élément électronique ainsi qu'élément optique
WO2015152302A1 (fr) * 2014-03-31 2015-10-08 コニカミノルタ株式会社 Film barrière contre les gaz, procédé de production associé, dispositif électronique utilisant ledit film et procédé de fabrication de dispositif électronique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021199798A1 (fr) * 2020-03-31 2021-10-07 東洋紡株式会社 Stratifié à base d'un substrat inorganique/film plastique technique équipé d'un film protecteur, empilement stratifié, procédé de stockage de stratifié, et procédé de transport de stratifié
JP6962506B1 (ja) * 2020-03-31 2021-11-05 東洋紡株式会社 保護フィルム付きの無機基板／エンジニアリングプラスチックフィルム積層体、積層体のスタック、積層体の保管方法、および積層体の輸送方法

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